Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
  • C07F15/0073—Rhodium compounds
  • C07F15/008—Rhodium compounds without a metal-carbon linkage

Definitions

• the present invention refers to a process for the preparation of ⁇ -3-carbopentazane-N 1 , N 4 :N 2 ,N 5 -bis[bis(triphenylphosphine)rhodium (I)] dinitrate.
• This compound was previously described in European Patent Application No. 87 304 279.0 (Publication No. 0 283 616), wherein it was shown to be a stereospecific homogeneous hydrogenation catalyst, especially in the hydrogenation of the exocyclic methylene group of acid addition salts of 6-demethyl-6-deoxy-6-methylene-5-hydroxytetracycline (methacycline) to prepare ⁇ -6-deoxy-5-hydroxytetracycline (doxycycline).
• this compound can be prepared by reacting tris(triphenylphosphine)nitratorhodium (I) with hydrazine in methanol.
• a process for the preparation of ⁇ -3-carbopentazane- N 1 ,N 4 :N 2 ,N 5 -bis[bis(triphenylphosphine)rhodium (I)] dinitrate characterised by the fact that tris(triphenylphosphine)nitratorhodium (I) is reacted with hydrazine in degassed methanol under an inert atmosphere.
• tris(triphenylphosphine)nitratorhodium (I) has been described in British Patents Nos. 1,368,432 and 1,368,433.
• the preparation involved protonation of rhodium (II) acetate in methanol with 40% fluoroboric acid at 60° C. for about 16 hours.
• the resulting green solution was then treated with a saturated methanolic solution of triphenylphosphine to give an orange solid, identified as tris(triphenylphosphine)rhodium (I) fluoroborate.
• the starting tris(triphenylphosphine)nitratorhodium (I) can be prepared by this process.
• it can be prepared by reacting at reflux 1 mole of rhodium trinitrate dihydrate with 6 moles of triphenylphosphine in ethanol or methanol.
• the red crystals were shown to be ##STR2## by X-ray crystallography and infra-red spectroscopy.
• the melting point was 120° C., identical with that quoted in British Patents Nos. 1,368,432 and 1 368,433.
• the reaction time was much shorter, typically of the order of one hour.
• a first yellow precipitate was filtered off and the red filtrate was allowed to stand at room temperature.
• the red crystals so formed, were filtered and dried.
• the yellow microcrystalline precipitate has not been structurally identified.
• the red crystals have been confirmed to be tris(triphenylphosphine)nitratorhodium (I) by X-ray crystallography.
• the amount of hydrazine used was between 3 and 6 moles per mole of tris(triphenylphosphine)nitratorhodium (I), preferably between 4 and 5 moles.
• the reactants were refluxed together overnight, preferably for 16 hours under an inert atmosphere, such as nitrogen. Upon standing, orange crystals were deposited, which were filtered off and dried under vacuum or under an inert atmosphere.
• Rhodium trinitrate dihydrate (2.15 g; 7.02 mmoles as rhodium) was dissolved in 95% ethanol (60 ml), under a nitrogen atmosphere, in a two-necked round bottom flask.
• the compound was thus formulated as bis(triphenylphosphine)carbonyl-nitratorhodium (I), for which the calculated elemental analysis is C 61.94%; H 4.21%; N 1.95%; and P 8.63%.
• This formulation and a trans-phosphine structure was confirmed by X-ray crystallography.
• Rhodium trinitrate dihydrate (0.215 g; 0.70 mmoles as rhodium) was dissolved, under a nitrogen atmosphere, in a two-necked round bottom flask, in the minimum quantity of methanol to give a clear solution.
• a hot solution of triphenylphosphine (1.051 g; 4.01 mmoles) in methanol (30 ml) was added. After refluxing under nitrogen for 1 hour, a yellow precipitate was deposited in a deep red solution. The precipitate was filtered off and, on standing, the red filtrate deposited red crystals, which were shown to be tris(triphenylphosphine)nitrtorhodium (I), identical with those obtained by the method given in Example 1.
• Tris(triphenylphosphine)nitratorhodium (I) (0.20 g; 0.21 mmoles) and hydrazine (3.0 ml of a methanolic solution containing 1.00 ml/100 ml; 0.95 mmoles) were mixed in dry. degassed methanol (30 ml). The mixture was refluxed overnight (16 hours), and then cooled to room temperature. The orange crystals that formed were filtered and dried.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Cephalosporin Compounds (AREA)
• Inorganic Compounds Of Heavy Metals (AREA)
• Saccharide Compounds (AREA)

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Citations (13)

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• 1989
  • 1989-07-31 PT PT91333A patent/PT91333B/pt not_active IP Right Cessation
• 1990
  • 1990-07-26 US US07/558,058 patent/US5075470A/en not_active Expired - Lifetime
  • 1990-07-30 AT AT90308327T patent/ATE111103T1/de not_active IP Right Cessation
  • 1990-07-30 ES ES90308327T patent/ES2064647T3/es not_active Expired - Lifetime
  • 1990-07-30 EP EP90308327A patent/EP0411854B1/de not_active Expired - Lifetime
  • 1990-07-30 DE DE69012254T patent/DE69012254T2/de not_active Expired - Lifetime

Patent Citations (16)

Non-Patent Citations (3)

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